Nitrosobenzene-Mediated C−C Bond Cleavage Reactions and Spectral Observation of an Oxazetidin-4-one Ring System

While bond formation processes have traditionally garnered the attention of the chemical community, methods facilitating bond breaking remain relatively undeveloped. We report a novel, transition-metal-free oxidative C−C bond cleavage process for a broad range of ester and dicarbonyl compounds invol...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2008-09, Vol.130 (37), p.12276-12278
Main Authors: Payette, Joshua N, Yamamoto, Hisashi
Format: Article
Language:English
Subjects:
Azetidines - chemistry
Carboxylic Acids - chemistry
Esters - chemistry
Nitroso Compounds - chemistry
Oxidation-Reduction
Spectrophotometry, Infrared - methods
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Summary:While bond formation processes have traditionally garnered the attention of the chemical community, methods facilitating bond breaking remain relatively undeveloped. We report a novel, transition-metal-free oxidative C−C bond cleavage process for a broad range of ester and dicarbonyl compounds involving carbanion addition to nitrosobenzene. ReactIR experiments on the nitrosobenzene-mediated oxidative decarboxylation of esters indicate the reaction proceeds via fragmentation of a previously unobserved oxazetidin-4-one heterocycle, characterized by an intense IR stretching frequency at 1846 cm−1. These mechanistic studies have allowed further expansion of this protocol to ketone cleavage reactions of a diverse array of β-ketoester and 1,3-diketone substrates. The conceptual and mechanistic insights offered by this study are likely to provide a platform for further development of bond-breaking methodologies.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja804325f